New water-soluble dyestuffs of the thioxanthone and acridone series



nited States Patent 2,993,045 a NEW WATER-SOLUBLE DYESTUFFS OF THE THIOXANTHONE AND ACRIDONE SERIES Max Staeuble, Base], and Kurt Weber, Bottmingen, Switzerland, assignors to Ciba Company, Inc., Fair Lawn, N .J 7 No Drawing. Filed Dec. 13, 1957, Ser. No. 702,510 Claims priority, application Switzerland Dec. 18, 1956 11 Claims. '(Cl. 260- -249) This invention provides new water-soluble dyestuffs,

which contain, in addition to at least one group imparting solubility in water and an at least monohalogenated 1:3 :5- triazine radical, a heterocyclic six-membered ring toboth sides of which are fused aromatic nuclei and which ring contains a keto group and as the sole heteroatom a sulfur or nitrogen atom in para-position to the keto group.

These dyestuffs are made by condensing a trihalogen- 1:3:5-triazine, especially cyanuric chloride (2:4:6-trichloro-1:3:5-triazine), with an advantageously watersoluble dyestufi which contains an acylatable amino group As dyestuffs of the aforesaid kind there may be used as starting materials dyestuifs of the acridone, benzophenonesulfone and especially thioxanthone series. In addition to an acylatable amino group the dyestulfs used as starting materials advantageously contain at least one strongly acid group imparting solubility in water, such as a carboxyl group or especially a sulfonic acid group. 1

The dyestuffs used as starting materials therefore contain with advantage the basic structure of the formula in which R and R each represent an aromatic radical, advantageously of the benzene or naphthalene series, fused on to the heterocyclic ring at the positions indicated by valency bonds, and X represents a sulfur atom which may be hexavalent as, for example, in the SO;,- group, or a nitrogen atom. In these dyestuil's the acylatable, that is to say, primary or secondary, amino groups and, if desired, further substituents may be present in an external nucleus, that is to say, in a nucleus which is bound to one of the radicals R and R through an oxygen atom, a CO-- or -CO group, a carboxylic acid amide group, or a sulfonic acid amide group or advantageously an NH group, as is the case in aminophenylaminoacridones or -thioxanthones. It is of advantage to use dyestuffs of this type which contain in the external nucleus a group imparting solubility in water, if the radicals R and R are free from such groups. The reactive amino As dyestuifs to be used as starting materials there may be mentioned, for example, those of the formula NH: o0

group. To this end there are used as starting material dye- 2,993,045 Patented July 18, 1961 ice group, and especially thioxanthone dyestuifs, such as amino-'thioxanthone sul-fonic acids of the formulae I NE:

NH 00 Q Hons SOsH and and the corresponding thioxanthone-S-dioxides.

The starting materials used in the process of this invention are obtained, for example, also by reacting sulfonic acid halides of acridone or thioxanthone dyestufis (such as are obtainable, for example, by treating the dyestuffs with chlorosulfonic acid or by reacting dyestufi sulfonic acids with acid halogenating agents such as phosphorus halides, thionyl chloride or chlorosulfonic acid) with organic compounds which contain an acylatable group, especially an acylatable amino group, and which contain in addition to the acylatable group, a further acylatable amino group or a substituent capable of being converted into sucha group after the reaction with the dyestuii sulfonic acid halide. As such organic compounds there may be used bifunctional organic compounds such as diarnines, for example, cyclic, and especially aromatic, di-amines such as 4:4'diamino-diphenyl, 4:4'-diaminostilbene-2:2'-disulionic acid, 1:4- or 1:3-diaminobenzene and above all 1:4- di-aminobenzene-Z-sulfouic acid and 1:3-diaminobenzene- 4-sulfoni'c acid. There may also be used nitraniline or monoacyl-derivatives of organic diamines followed, after the reaction with the dyestufi sulfonic acid chloride, by reduction or hydrolysis to form a new NH group. Care must be taken by choosing the starting materials that the-product obtained contains at least one acylatable amino group and at least one carboxyl or sulfonic acid fonic acid halide of the above kind, containing at least two such groups.

The dyestuffs containing acylatable amino groups are condensed in the .process of this invention at their amino groups with trihalogen-1:3:-5-triazine compounds or with dihalogen-triazines of the formula H-Halogen Halogen obtainable therefrom, in which formula Y represents the radical of an organic hydroxyl-compound bound through its oxygen atom, or -an--NH group or the radical of an amine of dyestufl or non-dyestuff character bound through the amino group, advantageous'lyfthe"radical of such an amine containing a water-.solubilising group.

' The dihalogen-triazines of this composition can be obtained by methods in themselves known from cyanuric halides, such as cyanuric bromide or cyanuric chloride, for example, by reacting one mol of cyanuric chloride with 1 mol of an aminoorhy'droxy-compound of dyestufi or non-dyestufl character, for example, the .dyestufl? mentioned above or amino-anthraquinone dyestufissuch as are obtainable by condensing 1 amino-4ebromanthraquinone- 2-sulfonic acid with a diamine ora monoacyl-derivative of an aromatic diamine andzsubsequently hydrolysing the acyl group. As compounds of non-dyestuff character there may be mentioned, for example, ammonia, aliphatic or aromatic hydroxy-compounds, such as methyl alcohol, ethyl alcohol or butyl alcohol, phenol, ortho-, metaor para-cresol, '4-secondary butylphenol, 4-tertiary amylphenol, dialkyl-phenols,"para-chlorophenol and above all organic compounds of nitrogen, such as methylamine, dimethylamine,ethylamine, diethylarm'ne, -isopropylamine, butylamine, hexyl-amine, phenylamine, tolylamine, 4-chlorophenylamine, N-methyl-phenylamine or ethanolamine, acetamide, butyric acid amide, urea, thiourea, toluene sulfonic acid amide, glycine, amino-carbonic acid esters, such as the methyl or ethyl ester, amino-acetic.acidesters, .such as the methyl oroethyl ester, aminoacetamide, l aminoben zene-2- or 4-methylsulfone, -l-arriin'obenzene2:"S-disulfonic acid, aminobenzoic acids and sulfonic acids thereof, l-aminobenzene-2-, -3- or -4-sulfonic acid or sulfon-amides or sulfones thereof. The'primary condensationproducts so obtained contain two reactivehalogen atoms. Those whichcontain no sulfonic acid groups are condensed only with dyestuffs containing atleast one sulfonic acid, group, whereas'the primary condensation products of the .Formula '1 which contain one or two sulfonic acid groups in the radical Y may be reacted with dyestuffs of the afore said kind which are free'from sulfonic acid groups.

The condensation of the cyanuric chloride or offthe dihalogen-triazine compounds with the dyestuffs, contain ing acylatable groups, is advantageously carried outlin the presence of'anacid-binding agent, such as sodium acetate, sodium hydroxideor sodium carbonate, arid .under conditions such that the final product still contains atleast one exchangeable halogen atom, for example, in an organic solvent or'at a'relatively low temperaturejin an aquebus medium. j

The dyestuffs obtained bythe process ofthisinve'ntio'n are advantageously isolated :at'a low -temperature;"for example, by -salting out and filtration or by evaporating 4 carried out [at not too high a temperature and under reduced pressure. By spray drying the entire mixture resulting from preparation of the dyestufi it is possible in some cases to produce dry preparations directly, that is to say, without intermediate isolation of the dyestuft. By these methodsyaluable new dry preparations are obtained, which are suitable for the preparation of stock'solutions or dyebaths, or if desired, :printingpastes.

; The :dyestuffs .of this invention are new. They are valuable dyestuffs for dyeing or printing a very wide variety of materials, especially polyhydroxylated materials offibrous structure and also synthetic fibers, "for example, of regenerated'cellulose, and also natural materials, for example, cellulose, linen or above all cotton. They are suitable for dyeing .by the so-calleddirect dyeing method from an aqueous alkaline bath which may contain asalt in' high concentration, and above all by the printingor pad dyeing method, in whichthe dyestufi is applied .to .the material to be dyed by printing or foulardingand .fixed on the fiber by means of an acid-binding agent.

The dyeings produced with the new dyestuffs on .cellulose-containing fibers are .usually distinguished by the purity of their tints, by their good fastness to light above all'by their excellent fastness to Washing.

"The following examples illustrate the invention, the parts and percentages being by Weight unless otherwise stated, and the relationship of parts by weight to v.parts by yolume being thesame as that of the kilo-gram to the liter:

Example 1 HOaS is maintained between 6.0 and 7.5 by the dropwise additionofabout 55 .parts by volume of a 2 N-solution of sodium carbonate. After stirring the mixture tor /2 hour at ,04 C., the dyestufi is precipitated from the solution by the addition of sodium chloride and is filtered off. The dyestufl is advantageous Washed with a'solution of.5 parts of disodium phosphate, 3 parts of monopotassium phosphate and 30 parts of sodium chloridezin 200 parts of Water, then subjected to-strong suction on the filter, .and dried at 30-35 C. in vacuo.

Cotton orregenerated cellulose can be dyed withthe above dyestuff inthe following manner to yield yellow tints.of :good"fastness to chlorine, washing and light:

Zrparts'of the dyestuff are dissolved together with 80 a parts .of 'trisodium'phosphate in 400, parts of water-and themix-ture resulting fromlhepreparationof the-dyestuif. The. filtered dyestuffs may; if desired; be dried after-the addition .;o-f an extender, aand advantageouslyl'the .fdrying is of fastness. p v p Instead of trisodium phosphate, sodium carbonate can the mixture is diluted to 4000 parts. After the addition offparts of sodium chloride, parts of a cotton "fabric are entered into the dyebath, the temperature is. raised to 60 C. in /2 hour, and' a 'further '80 parts of sodium chloride are added, the temperature is increased to 80 C.=in the course of 4 hour, and the latterttemperature is maintained for /2 hour. Thematerial is then'rinsed and-soaped for-l5 minutes-in a-b oil ing solution of 0.3% strength of a non-ionic detergent, The yellow dyeing so obtainedhas excellent properties be used with equal-successin this example.

Example 2 SOaNa N I HOa ([3 100 parts of ice are added to a solution of 18.5 parts of cyanuric chloride in 80 parts of acetone. The suspension of cyanuric chloride so obtained is admixed with a solution cooled to 0 C., of 19.5 parts of the sodium salt of l-aminobenzene-3-sulfonic acid in 300 parts of water. 55 parts by volume of a 2 N-solution of sodium carbonate are immediately added dropwise to the mixture so as to maintain the pH value between 5.0 and 7.0, and the temperature is maintained between 0 C. and 4 C. by external cooling. There is obtained a clear solution of the primary condensation product of equimolecular proportions of cyanuric chloride and l-aminobenzene-3-sulfonic acid.

The solution so obtained is immediately poured into a solution of 34.3 parts of the sodium salt of 1-amino-4- methyl-thioxanthone sulfonic acid (prepared as described in Example 5 of French Patent No. 974,872, granted October 4, 1950, to The Anchor Chemical Company Limited), in 1000 parts of water, and 55 parts by volume of a 2 N-solution of sodium carbonate are added dropwise at 3540 C. so as to maintain the pH value between 5.5 and 7.5. The whole is stirred for 2 hours at that temperature, during which the pH value should remain at 7.0 to 7.5. The dyestufi so obtained is precip: itated by the addition of sodium chloride, filtered oif, washed with sodium chloride solution of 15% strength, and then dried at 80 C. in vacuo.

Cotton or regenerated cellulose is dyed a yellow tint of very good fastness to washing, chlorine and light in the following manner:

1 part of the above dyestuflf is dissolved in 100 parts of water. A cotton fabric is impregnated with the solu tion at 80 C. on a foulard, the excess of liquid is removed by squeezing until the material retains 75% of its weight of dyestufl? solution. The material so impregnated is dried and then impregnated at room temperature in a solution containing, per liter, grams of sodium hydroxide and 300 grams of sodium chloride, and the material is then squeezed to a weight increase of 75% and steamed for 60 seconds at 100-101 C. The material is then rinsed, treated in sodium bicarbonate solution of 0.5% strength, rinsed, soaped at the boil for A hour in a solution of 0.3% strength of a noniom'c detergent, rinsed and dried. There is obtained a yellow dyeing which is fixed fast to boiling.

Example 3 100 parts of ice are added to a solution of 19 parts of cyanuric chloride in 80 parts of acetone. The suspension of cyanuric chloride so obtained is admixed with a solution, cooled to 0 C., of 30 parts of the disodium salt of l-aminobenzene-Z:S-disulfonie acid in 330 parts of water. 55 parts by volume of a 2 N-solution of sodium carbonate are added dropwise so as to maintain the pH value constantly between 5.0 and 7.0 and the temperature is maintained at 04 C. There is obtained a clear solution of the primary condensation product of equimolecular proportions of cyanuric chloride and 1- aminobenzene-ZzS-disulfonic acid.

The solution so obtained is immediately poured into a solution of 34.3 parts of the sodium salt of 1-amino-4- methyl-thioxanthone sulfonic acid in 1000 parts of water, and 55 parts by volume of a 2 N-solution of sodium carbonate are added dropwise at 6070 C. so as to 7 maintain the pH value between 5.5 and 7.0. The re sulting dyestutf is precipitated by the addition of sodium chloride, filtered off, washed with sodium chloride solution of 20% strength and then dried in vacuo at 70-80 C.

Cotton or'regenerated cellulose can be dyed with the resulting dyestuflf by the method described at the end of Example 2 yielding tints of good fastness to washing, chlorine and light.

I Example 4 A solution of 6.8 parts of the sodium salt of 2:4-dichloro-6-phenylamino-l 3 :5-triazine-4'-sulfonic acid in parts of water are added to 100 parts of a neutral solution of the sodium salt of 5 parts of the sulfonated condensation product of 1:4-diaminoanthraquinone and thiosalicylic acid (prepared, for example, as described in Example 11 of French Patent No. 974,872, granted October 4, 1950, to The Anchor Chemical Company Limited). The whole is heated to 60-7 0 C. and mineral acid liberated during the condensation is neutralised by the gradual addition of 11 parts by volume of a 2 N-solution of sodium carbonate so as to maintain the pH value of between 5.0 and 7.0. The dyestufi is precipitated in the usual manner by the addition of sodium chloride; and is then isolated by filtration and dried in vacuo at 70 C.

Cotton or regenerated cellulose is dyed grey tints of good fastness to washing by the method described at the end of Example 1.

By using in this example, instead of 6.8 parts of the sodium salt of 2z4-dichloro-6-phenylamino-1:3 :S-triazine- 4'-sulfonic acid, the same quantity of the sodium salt of 2:4 dichloro-6-phenylamino l:3:5-triazine-3-sulfonic acid, there is obtained a dyestutf having similar properties.

Example 5 3.8 parts of the sodium salt of a-amino-naphthothioxanthone sulfonic acid (prepared as described in Example 7 of French Patent No. 974,872, granted October 4, 1950, to The Anchor Chemical Company Limited), are dissolved in 100 parts of water at 70 C., and then a solution of 3.4 parts of the sodium salt of 2:4-dichloro- 6-phenylamino-1:3:5-triazine-3-sulfonic acid in 50 parts of water is added. At a temperature of 6070 C. the

mineral acid liberated during the condensation is con- Example 6 o N N SOaH f sotn CH3 i 4.4 parts of the sodium salt of 1-(4'-aminophenyl amino)-4-methyl-thioxanthone .sulfonic acid of the prob able formula "7 are dissolved in 100 parts of water, and then thesolution is poured into a solution of 3.4 parts of the sodium salt of 2:4 -dichloro-6-phenylamirio-1:3:5-triazine-3'-sulfonic acid in 100 parts of Water. Theeondensation is carried out at 60-70" C., and the mineral acid split oif is neutralised by the gradual addition of a total of 10 parts by volume of a l N-solution of sodium hydroxide so as to maintain a pH value between 5.0 and 7.0.

The dyestufl? is precipitated by the addition of sodium chloride at room temperature, and then isolated by .fi1 tration and dried in vacuo at 70 C.

Cotton or regenerated cellulose is dyed by the dyestu'tl red brown tints of very good'fastness to Washing by the method describedat-the end of Example '2.

The 1-(4'-aminophenylamino)-4-methyl thioxanthone sulfonic acid. used as starting material is obtained as follows: parts of lz4-diarninobenzene are dissolved in 50 parts of dimethyl aniline, and maintained at a gentle boil-with 4.4 parts of 1-chloro-4-methyl-thioxanthone-for 5 hours at 185 190 C. The solvent is then expelled with steam and the residue is filtered while hot. The crude 1-(4-aminophenylamino) -4-methyl thioxanthone can be purified by'recrystallisation'from dioxane, whereby-the pure productis obtained in the form of red-brown crystals. For sulfonation the product is heated in 12 times its Weight of oleum containing of S0 for 2 hours at 100 C., and 1-(4-aminophenylamino)-4-methylthioxanthone sulfonic acid is isolated by'pouring the sulfonation mixture on to sodium chloride solution of 10% strength and then filtering. By neutralising the filter residue with dilute sodium hydroxide solution there is obtained the corresponding sodiumsalt of l-(4'-aminophenylamino -4-methyl-thioxanthonesulfonic acid.

4.7 parts of the sodium salt of l-(4'-aminophenylamino) -4-nitro-thioxanthone sulfonic acid of the probable formula are dissolved in 100 parts of water, and condensed with 2.4 parts of the sodium salt of 2:4-dichloro-6-pheny1- amino-l:3:5-triazine-3'-sulfonic acid as described in Example 6. V There-1's obtained a dyestuff which dyes, by the'method described in Example 2, cotton or regenerated cellulose violet-brown tints of very good fastness to washing.

The. l-(4'-aminophenylamino) 4 nitro thioxanthone 'used in this exampleis obtained byv condensing l-chloro- 4-nitro-thioxantl1one and an excess of 1:4-diaminobenzene in boiling dioxane. The new compound crystallises from aqueous pyridine in brown-red crystals. For the purpose of sulfonation the compound is treated withv oleum containing 10% of SQain the manner described v75 in the last paragraph of Example"6.

.185 parts of 'cyanuric chloride are dissolved ill parts of acetone .and:the solution is pouredinga finestream into 250 parts ofice water, while stirringawell. Into'the cyanurict'chloride suspension is run .a solution, vcooledto 0 C., .of 42 parts of the sodium salt of :l-phenylamino- 4-amino-thioxanthone,sulfonic acid in 1000 parts of water and ;the pH :value is maintained between :5 .0 :and 7.0:by the .dropwise addition of a total of 5.5 parts by Volume oflag2 N-solution ;of;,so,dium carbonate at.a.ternperaturc of 24 C. The dyestufl is precipitated by :the addition of sodium chloride and filtered off. 7

The filter residue is, advantageously washed :withLasolution of :5 parts .of disodium phosphate, ,3 partsof monopotassium phosphate and .3.0 parts .of sodium;chlori de in 200parts of .water, and then subjected tostron-g suction, and driedin vacuo at,3 0.40 C;

The dyestufi, inits dry state is a yellow powderwhich dyes .cotton or "regenerated cellulose orange-yellow tints which aregfastto washingand light,,as follows:

2;parts.of:the dyestuff are dissolved inthercold in 2.000 I parts of water. There are then added ,parts .of-a sodimn carbonatesolutionlof 10% strength and 250parts of asodium chloride solution of 20% strength. .100 parts 'of well wetted cotton yarn are entered into .the resulting dyebath at,20-30 C., and a further 25.0 parts of a solution ofsodium chloride of 20% strength are added after 30 minutes. Dyeing is continued for aimther 60 minutes at,25e35 C. The reddish yellow dyeing so obtained is then rinsed with cold water and dried.

. amino-4-amino thioxanthone,sulfonic acid is isolated by introducing the sulfonation mixture into sodium chloride solution of 10% strength.

' 7 Example '9 g 5 parts of a solution of the ,sodiumsalt of l -(4.'-aminophenylamino) -4-nitro-thioxanthone S dioXide sulfonic acid of the probable formula in 100-parts of water: are condensed with 3-4 parts. ,of

ple 6 and isolated. 1

Example 1 S 0 aH O NH S 0 311 S /N NH(7 (ii-NH N\ N il/ CI 4.2 parts of the sodium salt 1-pheny1amino-4-aminothioxanthone sulfonic acid are reacted with 3.4 parts of the sodium salt of the condensation product of equimolecular quantities of cyanuric chloride and l-aminobenzene-3-sulfonic acid, that is to say, 2:4-dichloro-6- phenylaminod:3:-5-triazine-3'-sulfonic acid, as described in Example 6.

There is obtained a dystufi which dyes cotton and regenerated cellulose by the method described at the end of Example 2 clear orange-yellow tints of good iastness t light and washing.

Similar dyestuffs are obtained by using in this example, instead of 1-aminobenzene-3-sulfonic acid, l-aminobenene-Z-sulfonic acid or 1-aminobenzene-4-sulfonic acid or corresponding quantities of l-aminobenzene-pZzS-disulfonic acid or 2-aminonaphthalene-6-sulionic acid or 2-amino naphthalene-4; 8-disulfonic acid.

Example 11 1 NH 3 (I NH 00011 To a solution of 1.9 parts of cyanuric chloride in.10 parts of acetone 12 parts of ice are added while stirring. The resulting fine suspension of cyanuric chloride is then poured-into .a solution, cooled to 0 C., of 1.4 parts of 4- aminobenzoic acid in 40 parts of water and parts by volumeof a 11 N -solution of sodium hydroxide. The whole is stirred at a'pH value of 6.0 to 7.0 until aminobenzoic acid can no longer be detected.

Into the resulting condensation products of equimolecular; proportions of cyanuric chloride and 4-aminobenzoic acid is run a solution of 4.2 parts of the sodium salt of 1-phenylamino-4-aminothioxanthone sulfonic acid in 200 partspf water. At 60-70" C. the pH value is maintained cpntinuously between 6.0 and 7 .5 to the end of the ,con-

10 densation by the gradual addition of 5.5 parts by volume ofa 2N-solution of sodium carbonate. p 5 n By the addition of-sodiurn chloride the dyestufi is completely precipitated, and it is then isolated by filtration and dried in vacuo at 70 C.

, Cotton and regenerated cellulose are dyed by the methoddescribed inExample 2 orange-yellow tints of good fastness to washing and light. 7,

Similar dyestuifs are obtain d by using in this example, instead of 4-aminobenzoic acid, Z-aminobenzoicacid or 3-aminobenzoic acid.

Example 12 SOiH i 0 NH: O

100 parts of ice are added to a solution of 19 parts of cyanuric chloride in parts of acetone. The resulting suspension of cyanuric chloride is added to a solution, cooled to 3 C., of 53.3 parts of the disodium salt of 1- amino 4 (4 aminophenylamino) anthraquinone- 2:3-disulfonic acid in 2000 parts of water. At 3-5 C. and a pH value of 5.0 to 7 .0 a total of 50 parts by volume of a 2 N-solution of sodium carbonate is run in. When the monocondensation is complete a solution of 42 parts of the sodium salt of 1-phenylamino-4-amino-thioxanthone sulfonic acid in 2000 parts of water is added, and, while moderately heating the mixture to 5060 C., a further 50 parts by volume of a 2 N-solution of sodium carbonate is added dropwise to maintain the .pH value at 5.5 to 7.0. When the condensation is finished sodium chloride is added to the green dyestufi solution and the precipitated dyestutf is filtered off and dried in vacuo at 70-80 C.

The dyestufi dyes cotton and regenerated cellulose by the methods described in Examples 1 and 2 green tints of good fastness to washing and light.

Example 13 3.5 parts of the sodium salt of 1:4-diamino-thioxanthone sulfonic acid are dissolved in parts of water, and the solution is added to a solution of 3.4 parts of the sodium salt of 2:4-dichloro-6-phenylamino-1 :3 :S-triazine- 3-sulfonic acidin 100 parts of water. The condensation takes place very rapidly at 40-50 C. The mineral acid that splits oil is neutralized by the addition of 5 .5 parts by volume of a 2 N-solution of sodium carbonate while maintaining a pH-value of 5.0 to 7 .0.

By theaddition of sodium chloride the yellow dyestufi of the probable formula v r 11 iswprecipitated'in the usual-manner, isolated and-dried at 70 C. in vacuo.

It dyes cotton and regenerated cellulose by the methods described in Example 2 yellow tints of good fastness to washing and light.

Similar dyestuffs "are obtained by using in this example, instead a of 2:4-dichloro-6-phenylamino-1:3 :-triazine-3'-sulf0nic acid, 2z4-dichloro-6 phenylamino-l :3 :5- ttiazine lesulfonicgacid or 2:4-dichloro-6-phenylamino 1 :3 :5=triazine:2'-sulfonic acid.

.The 1:4-diamino-thioxanthone sulfonic acid used as starting material can be prepared as follows: l-chloro- 4-nitro-thioxanthone is dissolved in times its weight of nitrobenzene, and converted into 1-amino-4-nitrothioxanthone by introducing gaseous ammonia at 150- 160 C. By reducing the nitro group there is obtained the cor-responding diamino-compound. For the purpose of sulfonation the 1:4-diamino-thioxanthone is heated in 12 times its Weightof oleum containing 10% of S0 at 100 C. for one 'hour, and the resulting 1:4- diamino-thioxanthone sulfonic acid is isolated by pouring the sulfonation mixture into a sodium chloride solution of.l0% strength.

Example 14 18.5 parts of cyanuric chloride are dissolved in 80 parts of acetone, and the solution is run in the form of a fine jet into 250 parts of ice water, while stirring well. The cyanuric chloride suspension is then allowed to cool'to 0 C., a neutral solution of '35 parts-of the sodium salt of 1:4-diamino-thioxanthone sulfonic acid in 1000 parts of water is run in, and the pH value is maintained between 5.0 and 7.0 by adding dropwise 100 parts by volume of a 1 N-solution of sodium hydroxide at -a temperature of 2-4 S. 150 parts by volume of a 2N- solution of ammonium hydroxide .arethen slowly run in in such manner that the pH value does not exceed 8.5 and the temperature does not exceed 35 C.

By the addition of sodium chloride the dyestufi of the probable formula described in Example 2. .yellow tints of good fastness o washi g-an li Example-13 A solution of 19 parts of cyanuric chloride in 80 parts of acetone is added to a solution, cooled by the addition of ice to 0 C., of 35 parts of the sodium salt of 1:4- diamino-thioxane sulfonic acid in 1300 parts of water.

12 of sodium hydroxide. able formula is precipiated by the additionof sodium chloride, fil tered off and dried in vacuo at 70 C.

It'dyes cotton and .-regenera ted cellulose by the method described in Example 2 yellow tints of good fastness to washing and light.

Example 16 3.7 parts of the sodium salt of 1-ethylamino-4-aminothioxanthone sulfonic acid are dissolved in 100 parts of water, and condensed with anaqueous solution of 3.4 parts of thesodium salt of 2:4- dichloro-6-phenylamino- 1:3 :5-triazine-2'-sulfonic acid and isolated in the manner described in Example 6.

There is obtained a dyestuff of the probable formula which dyes cotton and regenerated cellulose by the method described in Example 2 yellow-orange nf good fastness to washing and light. a

The 1:ethylamino-4eaniino thioxanthone ,sulfonic acid used .as starting material can .be prepared, for example, by the method described in Example 13, :lastparagraph, but by the introduction of monoethylamine instead of gaseous ammonia.

The reaction mixture is stirred at 04..C., during which value is maintained between ;.5.0 and 7.0 by neutralization with a total of 100 parts by volumeof a 1 N solution condensation takes place yeryl-rapidlyat 40-50" amino')=4.-amino-thioxanthone sulfonic acid .are dissolved in-ELOOparts of water, and a solution of 6.8 parts of the sodium salt of -2:6dichlor0-6-phenylamino l:3:S-triazine-Bfi-sulfonicacid-in parts of-wateris added. The

while the mineral acid split 01f iscontinuously neutralized by' the addition of-=a total *of -10 -parts j-;by volume ose 2 N=so 1ution Qofsodium' carbonate so to {the pH-yalue-of'6:0 to-7;0. V V l Th'e d-yestufi issalted out from solution-with chloride, "filtered ofl anddrie'din' vacuo at 70 C. "Itdye's The yellow dyestutf of the pr obcotton and regenerated cellulose bythe methods described in Examples 1 and 2 yellow-brown tints of good fastness to washing.

The 1-(4-aminophenylamino)--4-amino 1 thioxanthone sulfonic acid used in this example is obtained from the 1-(4'-aminophenylamino)-4-nitro-thioxanthone described in the last paragraph of Example 7 by reduction of the nitro group followed v by sulfonation with sulfuric acid of 100% strength at 100 C. e

Example 18 3.2 parts of the sodium salt of l-amino-acridone sulfonic acid are dissolved in 100 parts of water and condensed with 3.4 parts of the sodium salt of 2:4-dichloro- 6-phenyl-amino-1 3 5 -triazine-3 '-sulfonic acid by the method described in Example 6 and isolated.

A dyestufi corresponding to the formula is obtained.

Cotton and regenerated cellulose are dyed by the method described in Example 2 yellow tints of very good fastness to washing.

The l-an'iino-aciidone sulfonic acid used as starting material is obtained from l-nitro-acridone (prepared according to Ullnrann, A 355, 332) by sulfonation with oleum containing 20% of S followed by reduction of the nitro group to the corresponding amino compound.

Example 20 SOaH 0 0 NH N SOaH NBC-0% (fi-NH 4 parts of the sodium salt of l-anilinM-amino-acridone sulfonic acid are dissolved in 100 parts of water and condensed with 3.4 parts of the sodium salt of 2:4- dichloro-6-phenylamino-1 :3 5-triazine-3'-sulfonic acid by the method described in Example 6 and isolated.

A dyestuff powder which is yellow-brown in its dry state is obtained which dyes cotton and regenerated cellu- 14' lose by ,the method described at the end of Example 2 orange-yellow tints of goodfastness to washing.

The 1-anilino-4 amino-acridone-sulfonic acid used in this example is obtained .by'reducing l-anilino-4-nitroacridone to l-anilinoA-amino-acridone and then sulfonating with sulfuric acid of 100% strength at 90 to 100 C.

What is claimed iszfl v 1. Water-soluble dyestufffof the formula wherein X is a member selected from the group consisting of --NH, SO;;-- and S; and Y is a member selected from the group consisting of H and wherein A is a member selected from the. group consisting of the chlorine atom, the ---NH;; group, the monosulfophenylamino, the disulfophenylamino, the monosulfonaphthylamino, the disulfonaphthylamino, the methand the carboxyphenylamino groups; and n is a whole positive number up to 2; said water-soluble dyestuif containing at least one and at most two oxy, the sulfophenoxy, the sulfoanthraquinonylamino groups, and said water-soluble dyestuff, addition to the last-mentioned group, containing a member selected from the group consisting of the sulfonic acid group and the carboxylic acid group.

2. Water soluble thioxanthone dyestufl of the formula /N\ G N\ V v so! m-l \C 7 u-lHjrl whereinX represents the sulfophenyl 0 group, Z represents the sulfonic acid group, and m and n each represents a whole number up to 2.

3. Water soluble thioxanthone dyestufl of the formula NE, co: (1 son:

wherein X represents the sulfophenylamino group.

1' '16 4. zWaterEol-uble thioxanthone dyestufl of theformula 9. Th'dyeStufl ofthe formula I v HN R JEN-(3X -1:

10 51 wherein X and R eaqhmeprqsents ,the sulfophenylamino group. 1

5. The dyestufi of the formula 10. The dyestuflf of the formula 01 E0111 7 soan NH CH:

6. The dyestufipf th'eforumla NH O H;

- N -0 SOaH NHC .o,o1 ('31 50m 'I ll K Ni f 1 E 1. The d estufi-of the formula y 11. 'Ihevdyestufl of the formula v V NE-(f \ENH SOzH Co N I r HOaS II IE NH 7 01- 180111 V r Rlefe'rences cited in the ;file of this patent i V V UNITED STATES PATENTS 3 dyesflfiflftheffirmula -1 ;719 792 'Ackermann v Ju1y"2, 1929 9 FOREIGN-PATENTS NH /N\ V 5 237,872 Great Britain Jan. 14," 1926 IT OTHER REFERENCES r LubS: The Chemistry of Synthetic Dyes and Pigments, V pp. 534-541; ASC Monograph 127 ,;Reinl}o1d Pub1ishing i $1; m N no Corp. (1955). 7

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,993 O45 July l8 1961 Max Staeuble et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 68 to 71 the formula should appear as shown below instead of as in the patent:

CO N112,

column 4, line 53, for "advantageous" read advantageously line 71 for "detergent read detergent. column 9 line 36 for "dystuff" read dyestuff column l1 line 35 for "2-4" 3.," read 24 C. a

Signed and sealed this 20th day of February 1962,

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

1. WATER-SOLUBLE DYESTUFF OF THE FORMULA
 9. THE DYESTUFF OF THE FORMULA 